Certain amine-modified thermoplastic phenol-aldehyde salts and method of making same



United States Patent CERTAIN AMINE-MODIFIED THERMOPLASTIC PHENOL-ALDEHYDE SALTS AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application January 2, 1953, Se-

rial No. 329,482. Divided and this application April 9, 1956, Serial No. 576,817

8 Claims. (Cl. 260-53) The present invention is a continuation-in-part of my two co-pending applications, Serial No. 288,742, filed May 19, 1952, now abandoned, and Serial No. 296,083, filed June 27, 1952, now U. S. Patent 2, 679,484, and a division of my co-pending application Serial No. 329,482, filedlanuary 2, 1953, now U. S. Patent 2,771,440.

My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

My aforementioned co-pending application, Serial No.

288,742, filed May 19, 1952, is concerned with the process of condensing certain phenol-aldehyde resins, therein described in detail, with certain basic non-hydroxylated secondary monoamines, also therein described in detail, and formaldehyde.

The present invention is'concerned with the aforementioned amino resin condensate in the form of a gluconic acid salt, i. e., a form in which all or part of the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

My aforementioned co-pending application, Serial No. 296,083, filed June 27, 1952, is concerned with a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of the amine resin condensates described in the aforementiond application Serial No. 288,742.

Needless to say, all that is required is to prepare the amine resin condensates in the manner described in the two aforementioned co-pending applications, and then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products go for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient hydrophile character to meet at least the test set forth in U. S. Patent 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally Xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all or part of the basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be Xylenesoluble. If such compounds are not Xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether or a low molal alcohol, or a mixture to dis- ,839,497 1C6 Patented Jun solve the appropriate product being examined and then mix with the equal weight of xylene, followed by addi tion of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into seven parts:

Part 1 is concerned with the general structure of the amine-modified resins which are converted. into the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary amines free from a hydroxyl radical which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concerned with the reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds which are neutralized subsequently with gluconic acid;

Part 5 is concerned with the conversion of the basic condensate into the corresponding salt of gluconic acid;

Part 6 is concerned with the resolution of petroleum emulsions of the Water-in-oil type by means of the previously described chemical compounds or reaction products in the form of gluconic acid salts; and

Part 7 is concerned with uses for the products herein 1 described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-cil type. This part is limited also to the use of the gluconic acid salts.

For reasons which are obvious, particularly for convenience and ease of comparison, Parts 1, 2, 3 and 4 are in substantially verbatim form as they appear in the two aforementioned co-pending applications, Serial Nos. 288,742, and 296,083, and particularly as they appear in the latter.

PART 1 in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and 1 generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

RI HN/ 3 in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not be a negative radical, which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. Needless to say, the two occurrences of R may jointly represent a single divalent radical instead of two monovalent radicals. This is illustrated by morpholine and piperidine. The introduction of two such amino radicals into a comparatively small resin molecule, forinstance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom.

' Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one may prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to '6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat-stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

Although these condensation products have been prepared primarily with the thought in mind that they are precursors for subsequent reaction, yet as such and without further reaction, they have definitely valuable properties and uses as hereinafter pointed out.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a tem- '4 perature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperature going up to to C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one. can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process employed in the manufacture of the condensation product is not intended to "limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolv the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can 'be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in 'turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of :a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanationto avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, wa teninsoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula 11 represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in thelinstance of low molecular weight polymers where the total number of phenol nuclei varies from} 106, i. e., It varies from 1 to 4; R reprecents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. 8. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Ke'iser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R\ H OH I- 11 OHH /R fiti ii 1% *EF K R RI R n R As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

OH OH OH RIII RIII1 R R R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the lcind herein employed as reactants, is Well known. See previously mentioned U. S. Patent 2,499,368. Resins can 6 be made using an acid catalyst or basic catalyst or a cat alyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other Words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. bus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most. readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I M01. Wt. Ex- Position R of resin ample R of R derived a molecule number from-- (based on n+2) 2a Tertiary butyl Para... 3. 5 882. 5

3a Secondary butyl. Ortho... 3. 5 882. 5 5a. Tertiary amyl Para. 3. 5 959. 5 Mixed secondary Ortho... 3. 5 805. 5

and tertiary amyl. Propyl Para 3. 5 805. 5 Tertiary hexyl. 3. 5 1, 036. 5 Octy 3. 5 1, 190. 5 3. 5 l, 267. 5 3. 5 l, 344. 5 y 3. 5 1, 498. 5 Tertiary butyl- 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 Nonyl 3. 5 l, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1, 148. 5 Nonyl 3. 5 1, 456. 5 Tertiary butyl 3. 5 1,008. 5

. Tertiary amyi 3. 5 1, 085. 5 N onyl 3. 5 1, 393. 5 Tertiary butyl. 4. 2 996. 6

Tertiary amyl- 4. 2 1, 083. 4 any 4. 2 1, 430. 6 Tertiary butyl- 4. 8 1, 094. 4 Tertiary amy1... 4. 8 1, 189. 6 4. 8 1, 570. 4 1. 5 604.0 1. 5 653. 0 1. 5 588. 0

PART 3 As has been pointed out previously, the amine herein employed as a reactant is a basic secondary monoamine, and preferably a strongly basic secondary monoamine, free from hydroxyl groups whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine' and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylpropylamine, di'butyl amine, diamylamine, dihexylamine, dioctylsmine, and dinonylamine. Other amines include bis(1,3-dimethylbutyl)amine. There are, of course, a variety of primary amines which can be reacted with an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alpha-methylbenzylamine, or benzylamine itself, to produce a suitable reactant. Need less to say, one can use secondary amines, such as dicyclohexylarnine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexylamine, ethylbenzylamine, etc.

Another class of amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula in Which x is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of in plus in equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514 dated July 27, 1943, to Hester, and 2,355,337 dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such 021340 C2H4O (3211 0 CzHrO 0211401 Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Compounds so obtained are exemplified by (C2H OC H OC H NH C8H17OC2H4OC2H4OC2H4) NH (C H OCH CH (CH 0 (CH CHCH NH (CH OCH CH OCH CH OCH CH NH (CH OCH CH CH CH CH CH NH Other somewhat similar secondary amines are those of the composition as described in U. 5. Patent No. 2,375,659 dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546 dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. "Eran-1 include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alphamethylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by PART 4 The products obtained by the herein described proc esses employed in the manufacture of the condensation product represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diificult to actually depict the final product of the cogeneric mixture except in the terms of the process itself. The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos. 288,742 and 296,083, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and -6 overall nuclei. The resin so obtained in a neutral state had a light amber color. a

882 grams of the resin identified as 2a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 (1., and 146 grams of diethylamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution and 162 grams were employed, which were added in about 2 /2 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 20 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time, and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within 2 to 3 hours after refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to elimihate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in 9 the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. In other examples it varied from 24 hours to 36 hours. Time can be reduced by cutting low temperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

highertemperature if desired, particularly under a reflux condenser. After salt formation is complete, I have permitted the solution to stand for about 6 to 72 hours. Sometimes, depending on the composition, there is some separation of an aqueous phase. On a laboratory scale, this procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, the aqueous phase is discarded and the solution can be brought back to a predetermined concentration by the addition of a hydrocarbon solvent, such as xylene, or by the addition of an alcohol, such as methyl, ethyl or propyl alcohol; or, if need be, one can employ a bridge solvent having hydrotropic properties in case of the diethylether of ethylene-glycol, or similar solvents.

The gluconic salts can be obtained in non-aqueous solution by using a slightly modified procedure. The procedure depends on the fact that the phase-separating trap can be used but it is preferable to stay below 150 C. so as to avoid any possible decomposition.

The xylene solution of the condensate, as previously described, is subjected to cacuum distillation so as to remove about one-half the xylene. Approximately twothirds of the xylene removed is replaced by benzene. This mixed solvent combination is subjected to refluxing TABLE II Strength of Reac- Reac- Max. Ex. Resin Amt. Amine used and amount formalde- Solvent used tion tion distill. N0. used grs. hyde soln. and amt. temp., time, temp.,

and amt. C. hrs. C.

882 Diethylamine, 146 grams 37%, 162 g. Xylene, 882 g. -25 150 480 Diethylamine, 73 grams 377 81 g..-- Xylene, 480 g. 22-30 24 162 633 30 100 g.. Xylene, 633 g- 21-24 38 147 441 Dibutylamine 129 grams 37%, 81 g Xylene, 441 g 25-37 32 149 480 .-.do do Xylene, 480 g-.. 20-24 149 633 dn do. Xylene, 633 g. 18-23 24 150 882 Morpholine, 174 grams" 7%, 162 Xylene, 882 g. 20-26 35 145 480 Morpholine, 87 grams 37%, 81 g. Xylene, 480 g 19-27 24 156 633 do d Xylene, 633 g 20-23 24 147 473 Dioctylamine (di-2-ethylhexylamine), 117 grams 30%, 100 g Xylene, 473 g.-- 20-21 38 148 511 do --d0 Xylene, 511 g.-- 19-20 30 146 665 do 37%, 81 g. Xylene, 665 20-26 24 150 441 (O2H600zH4002H-4)2NH, 250 grams 30%, 100 g.-. Xylene, 441 g.-. 20-22 31 147 480 do do Xylene, 480 g 20-24 36 148 595 (l0 37%, 81 g..- Xylene, 595 g 23-28 25 145 441 (OttH9OC1'I2CH(cHQ)O(CH3)OHO 2)ZNH, 361 grams do Xylene, 441 g 21-23 24 161 480 do do Xylene, 480 g.-. 20-24 24 150 511 d0 30%,-100 g Xylene, 511 g 20-22 25 146 498 (CHsOGHzCI-IzOCH2GH2OGH1CH2)2NH, 309 grams. 37%, 81 g. Xylene, 498 g 20-25 24 140 542 (i do Xylene, 542 g. 28-38 30 142 Xylene, 547 g- 25-30 26 148 Xylene, 441 g 20-22 28 143 595 l d0 0%, 100 Xylene, 595 g.-. 18-20 25 146 391 (OHaOOHzCHzGHzOHzOHzOHahNH, 98 gram 30%, g Xylene, 391 g- 19-22 24 145 PART 5 conic acid is a simple operation since it is nothing more nor less than neutralization. The condensates'invariably contain more than two basic nitrogen atoms. One can. neutralize either one, or both, basic nitrogen atoms.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts, at least not of the salts of the herein described condensates. Such salts appear to be stable, orstable for all practical purposes, at temperatures slightly above the boiling point of water and perhaps at temperatures as high as 150 C. or thereabouts.

For reasons pointed out previously, it is most convenient to handle the condensate as a solution, generally a solution in an inexpensive solvent, such as benzene, xylene, an aromatic petroleum solvent, or the like. A'number of the condensates previously described have been prepared in 50% solution as noted. Adding the calculated stoichiometric amount of 50% glyconic acid, calculated on the basis of the theoretical basic nitrogen atoms present, forms such salt which, in rnany instances may be slightly on the basic side and in other instances perhaps slightly on the acid side. The salt formation is merely a action under a condenser with a phase-separating trap. With the distillation point adjusted so as to be somewhere between to C. the mixture is refluxed and -ture at all times is left below C. At the end of the separation a suitable amount of solvent is added, or eliminated, by distillation so as to yield a. solution of predetermined concentration, for instance, 50%.

Using a somewhat similar procedure one can obtain the solvent-free material by merely subjecting the xylene solution of the condensate to vacuum distillation so as to remove all the xylene. The condensate itself is perfectly stable at C. or thereabouts and, thus, there is no particular danger of degradation involved in this step. The solvent-free material is then dissolved in ben zene instead of xylene and water eliminated in the manner previously described. The benzene is eliminated by vacuum distillation in such a way that the temperature never gets above 135 C. or 140 C. Actually, with care the solution previously described, to wit, the xylene-benzene solution, also can be removed without decomposition.

matter of agitating at room temperature, or somewhat 75 The solution of the salts varies in color from reddishamber to deep red or deep amber. Needless to say, if the condensate itself has been bleached by means of char, filtering clays, or the like, then the condensate salt is practically water-White or has a pale straw color. If de- 12 refining of petroleum, etc., may be employed as diluents; Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in consired, the solution of the salt can be bleached in a nection with conventional demulsifying agents. Moresimilar manner using filter chars, bleaching clays, or the over, said material or materials may be used alone or like. From a practical standpoint I have found no reason in admixture with other suitable Well-known classes of to decolorize the materials, or to prepare them in any demulsifying agents.

other than a solution form, using the cheapest solvents. It is well known that conventional demulsifying agents This applies particularly when this material is used as may be used in a water-soluble form, or in an oil-soluble a demulsifier for petroleum emulsions of the water-inform, or in a form exhibiting both oiland Water-sOluoil type, or oil-in-water type, or in the prevention of corbility. Sometimes they may be used in a form which rosion of metalic surfaces, particularly ferrous surfaces, exhibits relatively limited oil-solubility. However, since or as an asphalt additive for anti-stripping purposes. such r agents are frequently used 1n a ratio of 1 to In light of What has been said, and the simplicity of 10,000 1 B0 1 t0 even 1 to salt formation, it does not appear that any illustration 49,099 50,000 aslll desaltlng P Q P an is required. However, before referring to Table 111 which pp lnsohlblllty 011 and Water 18 fl i f p f ll i di t l h after r f n i d to E because said reagents undoubtedly have solubtllty w1th1n ample 1 such concentrations. This same fact is true in regard to Example 16 20 the material or materials of my invention when employed as demulsifying agents.

ThlS salt was made fromcondensate Example 1b. Ex- Th t i l of my invention, when employed as P 1b In fi Was mada from resin 2!! and dlethylatreating or demulsifying agents, are used in the convenmine. 882 grams of the resin dissolved in an equal welght tional way, well known to the art, described, for example, of xylene were reacted with 146 grams of diethylamlne in Patent 2,626,929, dated January 27, 1953, Part 3, and and 162 grams of 37% formaldehyde. Al this has been reference is made thereto for a description of conventiondescribcd previously. The weight of the condensate on al procedures of demulsifying, including batch, continua solvent-free basis was 1052 grams. This represented ous, and doWn-the-hole demulsification, the process esapproximately 27.8 grams of basic nitrogen. To this senti'ally involving introducing a small amount of demulsimixture, with constant stirring, there was added 780 fier into a large amount of emulsion with adequate adgrarns of 50% gluconic acid and stirring continued for mixture with or without the application of heat, and alone hour. The solution was poured into a separatory lowing the mixture to stratify. funnel, or yphon arrangement, and allcwed to tand at AS noted above, the pfOdUCtS herein described may be 40 C. for 3 days, A light amount of aqueous layer used not only in diluted form, but also may be used separated out at the bottom. Enough propyl l h l, admixed with some other chemical demulsrfier. A mixsomewhat l h 100 grams was d d to b i h ture which illustrates such combination is the following: final Weight to 2884 grams thus representing approxi- GlllCOIliC acid Salt, for p 1116 Product Of mately a 50% solution. ample 1c, 20%;

A number of other examples are included in Table Acyclohexylamine salt of a polypropylated napthalene III, following: monosulfonic acid, 24%;

TABLE III Condensate in turn derived fr0m- Salt formation Salt Salt from Wt. of Final ex. 0011- Aint. 37% conden- Theo. wt. ad- No. den- Resin Amt. sol- Amine formsate on basic glnjusted to sate No. resin, Solvent vent, Amine used used, a1de-* solvontnitroconic approx. N0. gms. gins. gms. hyde, free gen, acid, 50% salt,

gins. basis, gins. gms. 50% solv.,

gms.

1e...-. 1b 882 Diothylnrnine 146 162 1,052 27.8 780 2, 884 2c 20 7 81 565 18.9 390 1,520 3e..... 30 73 718 13.9 390 1, 820 46..... 4b 129 81 582 14.0 390 1,554 5e...-. 5b 129 81 621 14.0 590 1, 632 tie..-" 0b..... 129 81 774 14.0 390 1,938 7c 7b...-. 174 162 1,080 28.0 780 2,940 8c. 87 81 579 14.0 390 1,548 9e. 9b...-. 87 81 732 14.0 390 1,854 100..-. 10b.... 117 100 602 6.8 1,394 110.... 111).... 117 100 640 6.8 190 1,470 126..-. 125..-. 117 81 794 6.8 190 1,778 136.... 1b. 146 162 1,052 27.8 .190 2,494 14c 4b..... 129 81 582 14.0 1, 359 15c 7b M0rphline 174 162 1,020 28.0 390 2,430

1 30% sol.

PART 6 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as Water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particuiarly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol,

hexyl alcohol, octyl alcohol, etc., may be employed as diluents. 'iiscellaneous solvents such as pine oil, car- PART 7 The gluconic acid salts herein described can be used as emulsifying agents for oils, fats, and waxes; as ingredients bon tetrachloride, sulfur dioxide extract obtained in the 75 in insecticide compositions; or as detergents and Wetting i 13 agents in the laundering, scouring, dyeing, tanning and mordanting industries. They also can be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. Also, the gluconic acid salts are useful in dry cleaners soaps.

Also, they may be used as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic elfects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop rnicroorganic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growth of bacteria, molds, etc.; they are valuable additives to lu- 'bricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type; some have definite anti-corrosive action. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters.

Previous reference has been made to oxyalkylation, and particularly oxyethylation and oxypnopylation. The condensate prior to conversion into a salt is oxyalkylationsusceptible. Gluconic acid includes as part of its structure hydroxyl groups which are oxyalkylation-susceptible. Thus, it follows that the salt of the condensate contains one or more groups, indeed'a plurality of groups in which a labile hydrogen atom appears, and thus are in turn, oxyalkylationasusceptible. However, it is usually difficult, indeed extremely difiicult at times, to oxyalkylate in presence of :a radical which is in essence a salt as in the present case. For this reason it is more practical and more economical to convert the condensate into an oxyalkylated derivative and then convert the oxyalkylated derivative into a salt of gluconic acid. Such type of compound, or cogeneric mixture, is not within the scope of the present invention.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A two-step manufacturing process including the method of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei perresin molecule; said resin be ing difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable; and followed by neutralization with gluconicacid.

2. A two-step manufacturing process including the method of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable; and followed by neutralization with gluconic acid.

3. A two-step manufacturing process including the method of condensing (a) an oXyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 car bon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; With the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable; and followed by neutralization with gluconic acid.

4. A two-step manufacturing process including the method of condensing (a) an oxyethylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable; and followed by neutralization with gluconic acid.

5. A two-step manufacturing process including the method of condensing (a) an oxyethylation-susceptible, fusible, nonoxygenated organic solvent-soluble, waterinsoluble, low-stage phenobformaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between 21 difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 car- 16 bon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a sig nificant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable; and followed by neutralization with gluconic acid.

6. A two-step manufacturing process including the method of condensing (a) an oxyethylation-susceptible, fusible, nonoxygenated organic solvent-soluble, Waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5- phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; :said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being-formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants, be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylationsusceptible; and followed by neutralization with gluconic acid.

7. The method of claim 6 where R is substituted in the para position.

8. The product resulting from the process defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 1,996,069 Honel Apr. 2, 1935 2,031,557 Bruson Feb. 18, 1936 2,499,365 De Groote Mar. 4, 1950 

1. A TWO-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF CONDENSING (A) AN OXYALKLATION-SUSCEPTABLE, FUISIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 